Discharge Model for LiFePO4 Accounting for the Solid Solution Range

A comprehensive discharge model for LiFePO 4 electrode, including Li-ion diffusion in both the alpha and the beta solid solution phases, and phase transformation was developed. For the discharge model, the phase transformation, driven by the interfacial lithium concentration differences in both alpha and beta phases, was considered to be strongly dependent on the type of interface formed between the alpha and beta phases (coherent, semicoherent, and incoherent). By using the model as a tool, effects of extending the alpha and the beta solid solutions and reducing the particle size of LiFePO 4 on rate performance of LiFePO 4 were analyzed. The model developed in this article is applicable for predicting the discharge behavior of any other electrodes with phase transformation.

[1]  Yoshihiro Yamada,et al.  Electrochemical study on Mn2+-substitution in LiFePO4 olivine compound , 2007 .

[2]  Hsiao-Ying Shadow Huang,et al.  Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries , 2007 .

[3]  Peter Y. Zavalij,et al.  Reactivity, stability and electrochemical behavior of lithium iron phosphates , 2002 .

[4]  Jilt Sietsma,et al.  Evolution of the mixed-mode character of solid-state phase transformations in metals involving solute partitioning , 2006 .

[5]  R. Balasubramaniam Hysteresis in metal–hydrogen systems , 1997 .

[6]  Bruno Scrosati,et al.  A High-Rate, Nanocomposite LiFePO4 ∕ Carbon Cathode , 2005 .

[7]  Thomas J. Richardson,et al.  Electron Microscopy Study of the LiFePO4 to FePO4 Phase Transition , 2006 .

[8]  Linda F. Nazar,et al.  Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates , 2001 .

[9]  U. Nowark,et al.  A fully adaptive MOL-treatment of parabolic 1-D problems with extrapolation techniques , 1996 .

[10]  Robert Dominko,et al.  Is small particle size more important than carbon coating? An example study on LiFePO4 cathodes , 2007 .

[11]  Moving Boundary Model for the Discharge of a LiCoO2 Electrode , 2007 .

[12]  Yet-Ming Chiang,et al.  Electronically conductive phospho-olivines as lithium storage electrodes , 2002, Nature materials.

[13]  Christian Masquelier,et al.  Size Effects on Carbon-Free LiFePO4 Powders The Key to Superior Energy Density , 2006 .

[14]  Pedro E. Arce,et al.  A Discharge Model for Phase Transformation Electrodes: Formulation, Experimental Validation, and Analysis , 2007 .

[15]  Chunsheng Wang,et al.  Ionic/Electronic Conducting Characteristics of LiFePO4 Cathode Materials The Determining Factors for High Rate Performance , 2007 .

[16]  Wen Zhang,et al.  Using MOL to solve a high order nonlinear PDE with a moving boundary in the simulation of a sintering process , 1996 .

[17]  W. Craig Carter,et al.  Size-Dependent Lithium Miscibility Gap in Nanoscale Li1 − x FePO4 , 2007 .

[18]  Comparison of LiFePO4 from different sources , 2005 .

[19]  Robert Kostecki,et al.  Effect of surface carbon structure on the electrochemical performance of LiFePO{sub 4} , 2003 .

[20]  Yo Kobayashi,et al.  Apparent Diffusion Constant and Electrochemical Reaction in LiFe1 − x Mn x PO4 Olivine Cathodes , 2007 .

[21]  Jilt Sietsma,et al.  A concise model for mixed-mode phase transformations in the solid state , 2004 .

[22]  Donghan Kim,et al.  Synthesis of LiFePO4 Nanoparticles in Polyol Medium and Their Electrochemical Properties , 2006 .

[23]  L. Nazar,et al.  Nano-network electronic conduction in iron and nickel olivine phosphates , 2004, Nature materials.

[24]  B. W. Leitch,et al.  Accommodation energy of formation and dissolution for a misfitting precipitate in an elastic - plastic matrix , 1996 .

[25]  Venkat Srinivasan,et al.  Discharge Model for the Lithium Iron-Phosphate Electrode , 2004 .

[26]  F. Sommer,et al.  Kinetics of the abnormal austenite-ferrite transformation behaviour in substitutional Fe-based alloys , 2004 .